Hypochlorite bleaching compositions



United States Patent 3,172,861 HYPOCHLORITE BLEACHING COMPOSITIONS Alfred F. Steinhauer and Joseph C. Valenta, Midland, Mich., assignors to The Dow Chemical Company, Midland, Mich, a corporation of Delaware No Drawing. Filed May 25, 1961, Ser. No. 112,512 2 Claims. (Cl. 252-187) The present invention relates to novel and useful improved bleaching solutions. More particularly the present invention concerns the use of a novel surfactant in hypochlorite bleaching solutions to impart foaming and additional cleaning and bleaching power to such solutions.

It has now been found that an alkali metal salt of an alkylated diphenyl oxide sulfonic acid, when added in amounts of from about 1 to 100% by weight based on the active bleaching agent of a bleaching composition, will enhance bleaching, cleaning and brightening power of compositions of both household and industrial strengths. The desirability of adding a surfactant is increased since the foaming attendant with the use is an indication of the amount of bleaching solution added.

The alkylated diphenyl oxide sulfonic acid alkali metal salts and their nuclearly mono and dichlorinated derivatives, suitable for use in accordance with the present invention are those having from 8 to 22 carbon atoms in the alkyl chain and an average of from 1.8 to 2.3 sulfonate moieties per diphenyl oxide moiety.

The following examples illustrate the present invention but are not to be construed as limiting:

EXAMPLE 1 The solubility of 0.1% by weight of surfactant in aqueous sodium hypochlorate solutions at 25 C. for varioiis surfactants is recorded in Table I.

3,172,851 Patented Mar. 9, 1965 "ice Sodium pentadecyldiphenyl oxide disulfonate SC S: soluble, I:inso1uble, C: clear solution.

1 Ultrawet K, manufactured by Atlantic Refining Co.

3 lgiuponol ME, manufactured by E. I. du Pont de Nemours an o.

EDCUDOIIOI C, manufactured by E. I. du Pont de Nemours an 0.

* Stepan LDA, manufactured by Stepan Chemical Co.

5 Triton X100, manufactured by Rohm & Haas Co.

6 Tergitol O8, manufactured by Union Carbide Co.

Became cloudy with precipitate after 6 weeks shelf storage.

* Clear after 4 months shelf storage.

EXAMPLE 2 The surface tension of various concentrations of alkylated diphenyl oxide disulfonic acid, sodium salt, in aqueous 5% sodium hypochlorite solutions is reported in Table II below. The test solution was prepared from 27 ml. of aqueous 5% hypochlorite solution containing 0.2% or 0.4% by weight of a surfactant and 973 ml. of tap water having 70 ppm. hardness at 25 C.

Tabl II Concentration of Surfactant Surface Surfactant in Test Solu- Tension tion (Percent dynes by Weight) Sodium dodecyldiphenyl oxide disulfonate. 0. 0054 43. 0 D0 0. 0108 41. 1 Sodium pentadecyldiphenyl oxide disulfonate 0. 0054 46. 5 D 0 0. 0108 45. 5 No Surfactant 55.2

Table III 0 ompound Foam Height in mm. for Solutions After Standing 6 Weeks Before Foam Height in mm.

Testing Measurement Time, Minutes Measurement Time, Minutes Alkyl naphthalene sodium sulfonate 1 5 5 0 Sodium sulfate derivative of 2-ethyl-1-hexano1 30 0 Na dodecyldiphenyl oxide disullonate. 110 90 63 48 Na pentadecyldiphenyl oxide disulionate 135 118 115 110 Isooetylphenyl polyethoxyetha-ne 55 55 50 Na nonyl diphenyl oxide disulfonat 40 28 25 Na octyl diphenyl oxide disulionate 70 30 22 12 Na dodecyl monochlorodiphenyl oxide disul a 100 67 58 Na a-methylheptadecyldiphenyl oxide disulfonate. 85 78 72 65 Na monolauryldiphenyl oxide disulfonate 125 100 80 INCREASE SURFAOTANT CONC. TO 108 Sodium sulfate derivative of Z-ethyl-l-hexanol Na dodecyldiphenyl oxidedisulfonate Na pentadecyldiphenyl oxide (lisulfonate 1 Petro AA manufactured by Petrochemicals Co. 2 Tergitol 08.

3 Triton X100.

4 Sample was cloudy with precipitate.

Sample was shaken to disperse precipitate before test.

3 EXAMPLE 3 Two grams of one of several surfactants, e.g., sodium pentadecyldiphenyl oxide sulfonate, was added to 1000 grams of aqueous 5% hypochlorite solution (Clorox). Twenty-seven ml. of the above solution was added to 973 ml. water having a hardness of 70 ppm. as CaCO The above solution was then tested on the Ross-Miles Foam Tower. The test is carried out in the following manner.

One hundred cubic centimeters of a solution prepared in the above manner was pipetted into the Foam Tower directing the flow in such a way that it flows down the side Walls of the tower so as not to produce any foam. The same solution was placed in a dropping funnel, the stopcock opened, and the 200 cc. of solution allowed to fall into the 100 cc. of solution in the bottom of the tower. The height of the foam, in millimeters, was measured immediately and each minute of standing for a total of five minutes and the measurements recorded in Table III.

A second series of tests was carried out to determine the stability of the class of compounds of the present invention after standing for 6 weeks. The Ross-Miles Foam Tower test was carried out in the above manner and the results recorded in table III.

EXAMPLE 4 The following example illustrates the effectiveness of the surfactants in water of various hardnesses. The Ross Miles Foam Tower test was conducted in the manner of Example 2 using a solution prepared from 27 ml. of an aqueous 5% hypochlorite solution containing 0.2% by weight of sodium pentadecyldiphenyl oxide disulfonate and 973 ml. of water of various hardnesses. The results of such tests are indicated in Table IV.

It is to be understood that bleaching agents other than sodium hypochlorite can beenhanced in the foregoing manner. Some of such agents are the hypochlorites, i.e., sodium, potassium, calcium or magnesium hypochlorite, as well as chloride of lime (CaCl-Ca(ClO)).

We claim:

1. An aqueous 5 percent by weight sodium hypochlorite bleaching solution containing from about 1 to 100% by weight based on the active bleaching agent of a compound selected from the group consisting of alkali metal salts of an alkylated diphenyl oxide sulfonic acid and their nuclearly mono and dichlorinated derivatives having from 8 to 22 carbon atoms in the alkyl moiety and an average of from 1.8 to 2.3 sulfonate moieties per diphenyl oxide moiety.

2. An aqueous 5 percent by weight sodium hypochlorite bleaching solution containing from 1 to 100% by weight based on the active bleaching agent of a sodium dodecyl diphenyl oxide sulfonate having an average of about 2 sulfonate radicals per diphenyl oxide moiety.

References Cited in the file of this patent,

UNITED STATES PATENTS 2,415,657 Riggs et a1. Feb. 11, 1947 2,854,477 Steinhauer Sept. 30, 1958 2,992,999 Smith et al. July 18, 1961 

1. AN AQUEOUS 5 PERCENT BY WEIGHT SODIUM HYPOCHLORITE BLEACHING SOLUTION CONTAINING FROM ABOUT 1 TO 100% BY WEIGHT BASED ON THE ACTIVE BLEACHING AGENT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL SALTS OF AN ALKYLATED DIPHENYL OXIDE SULFONIC ACID AND THEIR NUCLEARLY MONO AND DICHLORINATED DERIVATIVES HAVING FROM 8 TO 22 CARBON ATOMS IN THE ALKYL MOIETY AND AN AVERAGE OF FROM 1.8 TO 2.3 SULFONATE MOIETIES PER DIPHENYL OXIDE MOIETY. 